Stereodefined Skipped Dienes through Iridium‐Catalyzed Formal Addition of Tertiary Allylic C−H Bonds to Alkynes

• Published in: Angewandte Chemie International Edition Vol. 61; no. 26; pp. e202200075 - n/a
• Main Authors: Wang, Zi‐Xuan, Gao, Peng‐Chao, Lin, En‐Ze, Li, Bi‐Jie
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 27.06.2022; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkene Isomerization; Alkynes; Allylic C−H Bond; Carbon; Chemistry; Chemistry, Multidisciplinary; C−H Cleavage; Dienes; Enantiomers; Hydrogen bonds; Iridium; Physical Sciences; Quaternary Carbon; Science & Technology; Skipped Diene; DISUBSTITUTED OLEFINS; SITE; Allylic C-H Bond; ISOMERIZATION; INTERNAL ALKYNES; Skipped Diene; Quaternary Carbon; C-H Cleavage; FUNCTIONALIZATION; ALKENES; AMINATION; STEREOCENTERS; Alkene Isomerization; ALKENYLATION; AMIDES; alkene isomerization; skipped diene; allylic C-H bond; C-H cleavage; quaternary carbon
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202200075

Preparation of skipped dienes with a quaternary carbon center at the C‐3 position remains a synthetic challenge. We report here an iridium‐catalyzed formal addition of tertiary sp3 C−H bond to alkyne for the facile preparation of skipped dienes. The tertiary allylic C−H bond is cleaved regioselectively, at the site of which a new C−C bond is formed. Enantioselective construction of acyclic quaternary carbon stereocenters is also demonstrated. An iridium‐catalyzed formal addition of allylic C−H bond to alkyne is reported. A tertiary C−H bond was cleaved at the site of which a quaternary carbon center was formed. This atom‐economical process provided a straightforward synthetic route to skipped dienes containing a C3‐quaternary carbon. Enantioselective construction of acyclic quaternary carbon stereocenters through enantio‐convergent vinylation of tertiary C−H bond was also feasible.